Silver alloys for use in medical, surgical and microsurgical instruments and process for producing the alloys

ABSTRACT

Alloys for medical, surgical and microsurgical instruments are proposed which comprise 0.01% to 20% by weight of germanium, from 0-25% of shallow hydrogenic and/or non-hydrogenic acceptor dopants in terms of weight ratio in relation to germanium, from 0% up to 20% by weight of one or more of the following compounds such as platinum, gold, palladium, iridium, ruthenium, osmium, rhodium, niobium, tantalum, tungsten, aluminium, silicon, hafnium, yttrium, lanthanum, zirconium with the remainder, up to 100% by weight, constituted by silver and inevitable impurities, wherein instruments from these alloys possess properties such as no capacitive impedance in relation to the electrode-tissue interface; a Far Infrared Radiation (FIR) emitting capacity when energized by any form of energy; sulfurization, corrosion and oxidation resistant and have suitable hardness for their intended use; emit anions and may possess fractal surfaces.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a continuation of prior filed copending U.S.application Ser. No. 10/726,100 filed Dec. 2, 2003 which claims thepriority of Italian Patent Application Serial No. PA 2003 A 000007,filed May 19, 2003, pursuant to 35 U.S.C. 119(a)-(d), and which claimsthe benefit of prior filed provisional application, Appl. No.60/499,469, filed Sep. 2, 2003, pursuant to 35 U.S.C. 119(e), thesubject matter of which is incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to noble metal alloys, and in particularsilver and/or gold alloys for use in manufacturing medical, surgical andmicrosurgical instruments. The present invention also relates to amethod of producing such alloys on the basis of silver and/or gold metalalloys.

BACKGROUND OF THE INVENTION

Pure metals and metal alloys which are generally composed of silver,gold, platinum, brass, steel, titanium, tungsten, palladium and the likehave long been used for personal ornaments, such as jewellery andsimilar. Likewise, such metals and alloys of such metals have also beenused in the field of dental medicine, for example, dental implants.Furthermore, such alloys are particularly important in the field ofmedicine for use in making surgical instruments. A number of alloys havebeen well known in the prior art.

U.S. Pat. No. 5,772,659 discloses an electrical generator which reducesthe severity of exit sparking by providing a quick response to highimpedance indications.

Furthermore, U.S. Pat. Publication No. 2002/0173787 discloses a bipolarelectrosurgical instrument for sealing blood vesicles and demonstratesthe necessity of using a no-sticking bipolar electrosurgical instrument.

In addition, U.S. Pat. Publication No. 2003/1076858 discloses anelectrosurgical instrument for cutting and/or coagulating tissue andteaches the use of one or more electrode surfaces at least partiallycoated with tungsten disulphide.

Furthermore, U.S. Patent publication No. 2003/0163125 discloses theutilization of an active catalyst in a surface coating of anelectrosurgical instrument.

Moreover, U.S. Patent publication No. 2003/0181904 discloses anelectrosurgical cutting and coagulation instrument. In addition, U.S.Pat. No. 1,970,319 discloses a tarnish resisting silver alloy made fromabout 85-93% silver, tin and up to 4% of either cadmium, antimony,copper, zinc, manganese and nickel-chromium.

Other prior art documents include; U.S. Pat. No. 3,669,655; U.S. Pat.No. 6,296,637; U.S. Pat. No. 6,293,946; U.S. Pat. No. 6,557,559; U.S.Pat. No. 6,506,267; U.S. Pat. No. 6,206,876; EP Pat. No. 0685565; GBPat. No 2,283,934; U.S. Pat No. 6,290,501; U.S. Publication No.2003/0050634; U.S. Publication No. 2002/0111622; U.S. Publication No.2003/0144653; WO 03/028669; U.S. Pat. No. 6,544,264, GB Patent No.2,255,348; WO 96/22400; GB Patent No. 2,033,425; U.S. Pat. No.6,406,664; WO 02/095082; U.S. Pat. No. 6,168,071; U.S. Pat. No.5,022,932; U.S. Pat. No. 5,039,479; U.S. Pat No. 6,011,810; U.S. Pat.No. 6,290,501; U.S. Pat. No. 6,139,652; U.S. Pat. No. 5,885,281; U.S.Pat. No. 5,925,039; U.S. Pat. No. 6,482,076; U.S. Pat. No. 6,533,781;U.S. Pat. No. 4,492,231; U.S. Pat. No. 5,037,708; U.S. Pat. No.4,775,511; U.S. Pat. No. 6,132,357; U.S. Pat. Publication No.2002/0187533; U.S. Pat. Publication No. 2002/0014050; U.S. Pat.Publication No. 2002/0010464; U.S. Pat. Publication No. 2002/0144956;U.S. Pat. Publication No. 2003/0139741.

All of the forgoing prior art documents disclose pure metal or metalalloys and/or surgical instruments.

Use of pure or nearly pure silver and pure gold or coating of silver andgold and their alloys on core structures, such as aluminium or copperfor manufacturing electro-surgical forceps and electrodes are also knownfrom U.S. Pat. No. 6,293,946 and U.S. Pat. No. 6,296,637.

Moreover, pure silver and gold metal or nearly pure silver and gold havea Vickers hardness (HVN) of about 30 as an ingot while having a HVN ofabout 54 when worked into a wire. It should be understood that thehardness measure in HVN is according to ASTM Spec. E 384-73, using a 200g load applied for 12 seconds varied as a function of the temperature atwhich age hardening occurs.

Alloys of pure silver and gold metal, as taught in the afore-statedpatents generally possess a satisfactory hardness for medical andsurgical instruments at least at the outset. However, instruments madefrom these metal alloys do not always retain their hardness over acourse of time due to their repeated exposure to heat during the courseof their use in, for example, when carrying out electro-surgery. Thus,it is very difficult to retain proper hardness over a long course oftime, specifically with respect to surgical instruments. Retaininghardness in surgical instruments as referred in the above-describedprior art patent documents is extremely difficult and the loss ofhardness is a major drawback in this physical criteria in theafore-stated patents.

Furthermore, the prior art references do not disclose or teach anyalloys that are suitable for medical, surgical and micro-surgicalinstruments and which possess a very low capacitive impedance withrespect to an electrode-tissue interface, nor does the prior artdisclose instruments that are able to emit far infrared radiation (FIR)used in the treatment of biological tissue in the medical field,specifically in the surgical field.

It would therefore be desirable and advantageous to provide improvedalloys for use in the production of electro-surgical instruments inorder to obviate prior art shortcomings. Such alloys should bebiocompatible and should be made from a non-stick material with highelectrical and thermal conductivity. Furthermore, such materials shouldhave appropriate hardness levels suitable for intended use, for examplefor surgical instrumentation. In addition, the alloys should be highlyresistive to tarnishing, and to oxidation and corrosion. Such alloysshould also have low capacitive impedance relative to anyelectrode-tissue interface while carrying out electro-surgicaltreatments.

In accordance with the present invention, noble alloys are proposed,essentially for use in manufacturing innovative medical, surgical andmicrosurgical instruments which possess high thermal and electricalconductivity, which are tarnish and corrosion resistant, and which havenon-stick properties, low capacitive impedance in relation to theelectrode-tissue interface and are damage-proof against scratching orrubbing, and that are extremely hard, with a Vickers hardness of 32 HVNor higher and that can emit far infrared radiation.

It is understood that the alloy according to present invention has farreaching applicability in areas other than medicine and/or applicationsas surgical instruments and can be used in any field, for example in thecomputer field or in chip technology where those characteristicsdescribed below and others are desirable.

SUMMARY OF THE INVENTION

In accordance with the present invention, the proposed noble alloys havea silver and/or gold alloy basis and posses the afore-stated propertiesdue to certain alloy components which when added to the melt renders thealloy extremely hard, as well as tarnish and corrosion resistant, and isultra electro- and thermo-conductive and biocompatible.

According to one aspect of the present invention, an alloy for use inmanufacturing medical, surgical, microsurgical and electrosurgicalinstruments includes from 0.01% to 20% by weight of germanium; between0% to 25% by weight relative to the germanium of at least one of anon-hydrogenic and shallow hydrogenic acceptor dopant; up to 20% byweight of one or more of the compounds selected from the groupconsisting of platinum, gold, palladium, iridium, ruthenium, osmium,rhodium, niobium, tantalum, tungsten, aluminum, silicon, hafnium,yttrium; lanthanum, zirconium and a remainder up to 100% by total weightconstituted by silver which includes impurities.

According to a feature of the present invention, the alloy is capable ofemitting anions. Furthermore, the alloy is resistant againstsulfurization and exhibits very low capacitive impedance relative to anelectrode-tissue interface and is able to emit far infrared radiationfor the treatment of biological tissue.

It is another feature of the present invention that the alloy containssemiconductor microcrystals in the form of p-type germanium quantum dotswhich renders the alloy suitable as constituent material for medical,surgical and micro-surgical instruments.

It is a further aspect of the present invention to provide a silver/goldalloy containing p-germanium microcrystals which is suitable as theconstituent material for medical, surgical and microsurgicalinstruments.

Following are certain features of the alloy according to the presentinvention, for example, when the alloy is used for surgical instruments.

For example, in connection with a surgical electrode, the alloy materialdoes not produce high capacitive impedance in relation to theelectrode-tissue interface during operation modes since theelectrode-tissue interface conduction is fully ohmic and interface isachieved by providing an electrode made from an alloy material havingembedded within its matrix p-type germanium quantum dot, certainsemiconductor microcrystals in the form of p-type germanium so that anyelectrical energy is conducted through movement of holes (electronvacancies) or electrons. Thus, when operating the electrode, no layer ofcations is able to form within the living biological tissue surroundingthe electrode and at the same time electrons do not collect at theelectrode surface.

The electrode and forceps according to the present invention used assurgical instruments maintain a low electrode-tissue interfacetemperature which prevents an impedance rise during radiofrequencyapplication at high power. In the alloy, according to the presentinvention, the conduction at the electrode-tissue interface is sustainednot by the solution phase ions movement but by the hole (electronvacancy) or electron movement.

Each of the metals, germanium and acceptor dopants used according to thepresent invention are safe materials to be used in contact withbiological living tissue.

The alloy contains metals which confer upon it appropriate degrees ofhardness, ductility and malleability. Germanium is known as ahardness-improving component.

The alloy can emit a large quantity of anions because germaniumcontained in the alloy material is a crystal having electricpolarization;

The surface of the instruments made from alloys according to the presentinvention can have a fractal geometry for a better energy distribution;

The alloy has excellent sulfurization, corrosion and oxidationresistance even under arduous conditions.

The alloy fully exhibits the far infrared radiation effect inherent inp-type germanium nanostructured microcrystals when the germanium elementis present in the alloy in a percentage from 0.9% to 9% by weight.

The alloy materials for medical, surgical and microsurgical instrumentsaccording to the present invention comprise the following acceptordopants: copper, gallium, indium, gold, platinum, zinc, and/or theiralloys. The silver alloys for medical, surgical and microsurgicalinstruments in accordance with the present invention comprise thefollowing metals and elements: platinum, gold, palladium, iridium,ruthenium, osmium, rhodium, titanium, niobium, tantalum, tungsten,aluminium, silicon, hafnium, yttrium lanthanum, zirconium and/or theiralloys. The alloys according to the present invention that are emittingfar infrared radiation can be energized by any form of energy. That is,the energy source can be electrical energy, radio frequency energy,ultrasonic energy, laser energy, thermal energy, magnetic energy, solarenergy, chemical energy, biological energy, human body energy, heat, orsimilar. Energy is provided to the far infrared radiation generatingp-type germanium quantum dot microcrystals embedded within the alloymatrix. Upon stimulation by energy, the transitions of energy levels ofthe p-type germanium microcrystals are emitted in the form ofelectromagnetic radiation to act on living tissue cells through weakradiation. When it matches with the strong absorption band of the celltissue, a large portion of the radiant energy carried by theelectromagnetic wave is absorbed, thereby causing changes of themolecular- or atomic- or electronic-energy in the living tissue cells,which then elicits oscillations which stimulates the cell energy tothereby increase the permeability of the cell membrane. Once the livingtissue cells have absorbed far infrared radiation then vibrationalmolecular resonance corresponding to the molecular state is causedinside the so-treated cells.

BRIEF DESCRIPTION OF THE PICTURES

Other features and advantages of the present invention will be morereadily apparent upon reading the following description of currentlypreferred exemplified embodiments of the invention with reference to theaccompanying Figures, in which:

FIG. 1 is a photo of an electrode made from a silver alloy according tothe present invention;

FIG. 2 is a photo showing soft palate cancer of a patient;

FIG. 3 is a photo showing an electrode in use during an operationshowing the no-stick effect of the electrode tip;

FIG. 4 is a photo showing a particular view of a muscular plain of thesoft palate;

FIG. 5 is a photo showing a microscopic specimen of an area with tissueremoved, wherein the edges appear smooth and the tissue well-preserved;

FIG. 6 is a photo showing how an uvula flap is created without anybleeding due to the utilization of the electrode according to thepresent invention, characterized by a very low capacitive impedance inrelation to the electrode-tissue interface and by a capacity to emit farinfrared radiation;

FIG. 7 is a photo showing a re-positioned flap, characterized by thetotal absence of thermal damage;

FIG. 8 is a photo showing histological connective tissue with irrelevantthermal damage (less than 6 microns);

FIG. 9 is a photo showing histological glandular tissue after removalusing low capacitive impedance (electrode-tissue interface) and farinfrared radiation technology;

FIG. 10 is a photo showing the superficial muscular plain of the palate,without any thermal damage;

FIG. 11 is a photo showing capillaries and fatty tissues, where there isabsolutely no thermal damage;

FIG. 12 is a photo showing an enlargement of 10× of histologicalspecimen of the bottom of the implant;

FIG. 13 is a photo showing muscular structure which remains intactwithout thermal damage;

FIG. 14 is a photo showing the edge of a section of a superficialepithelium with irrelevant thermal damage (less than 5 microns);

FIG. 15 is a photo showing a forceps made by the silver alloy (sampleno. 4) before coagulation of a vessel;

FIG. 16 is photo showing the same forceps as in FIG. 15 duringcoagulation.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The silver alloy electrode as shown in FIG. 1 according to the presentinvention contains germanium for use in medical, surgical andmicrosurgical instruments and contains up to 20% by weight (including0%) of one or more of the following metals and elements: platinum, gold,palladium, iridium, ruthenium, osmium, rhodium, rhenium, titanium,niobium, tantalum, tungsten, aluminium, silicon, hafnium, yttrium,lanthanum, zirconium.

Shown in FIG. 3 is the electrode in action during the resection of thenasal mucosal. As can be seen in FIG. 3, the electrode tip (arrow)exhibits a total absence of the “stick effect”.

The silver alloy containing germanium for use in the manufacturing ofmedical surgical and microsurgical instruments contains from 0.01% to20% by weight of germanium and must contain germanium in the range fromat least 0.9% to 6% by weight, more specifically from 1.1% up to 5% byweight. The said silver alloy materials according to the presentinvention comprise at least one of the said metals and elements inaddition to germanium and at least one non-hydrogenic and optionallyshallow hydrogenic acceptor dopant between 0% to 25% by weight relativeto the germanium. The said acceptor dopants should be present in thesilver alloy containing germanium in a weight ratio, which should be nohigher than 15% and no lower than 5% relative to the germanium content.According to the present invention, by melting the alloy elements,quantum dot semiconductor microcrystals ranging in dimensions between1000 angstrom and 10 angstrom, are embedded in a metal base or alloymatrix. Electron micrographs (×18,000) have demonstrated thatconsiderable nanometer-sized germanium microcrystal clusters areeffectively formed. The minute size germanium microcrystals result innew quantum phenomena that yield some extraordinary bonuses. Hence,these minute, semiconducting microcrystal quantum dots are gateways toan enormous array of possible applications and new technologies inmedical, surgical and microsurgical fields. These novel alloys representa system with challenging new physical properties. The semiconductor isgermanium and the acceptors used can be hydrogenic and/or non-hydrogenicacceptor dopants. The latter have much larger hole-binding energies thanhydrogenic dopants which result in the strong reduction of the internalabsorption of the generated far infrared radiation.

The non-hydrogenic dopants change the property of germaniummicrocrystals in the matrix of silver and at energies below the opticalphonon energy where far infrared radiation occurs.

Shown in FIG. 2 is a cancer of the soft palate; the arrows point to theextension. FIG. 4 shows a view of the muscular plain resectioncorresponding to the elevator of the palate.

Cells are made of uniquely-arranged atoms and molecules and themolecules are all moving among and between those atoms. When moleculesof mitochondria are irradiated with electromagnetic irradiation of about100 microns wavelength band, the electromagnetic wave energy is absorbedand the amplitude of the mitochondria's molecular vibration isincreased. The increased vibration produces heat through friction. WhenFIR (Far Infra Red), having the same vibration frequency ofmitochondria, an organelle within the cell, irradiates saidmitochondria, that organelle will filter out the FIR and experience aresonance absorption. This is a process known as resonance-absorption toheat-generation with aid of the FIR. The vibration of the cell atoms andmolecules will generate heat and result in resonance absorption. Theeffects generated by far infrared radiation reduce pain sensation bydirect action on both free-nerve endings in tissues and on peripheralnerves. Far infrared radiation, as a weak electromagnetic wave, has beenshown to lead to both increased endorphin production and a shutting downof the “spinal gate” (Melzack and Wall), each of which reduces pain.Electrodes made with the silver alloy according to the presentinvention, working in an electrosurgical RF (Radio Frequency) systeminvolve the explosive evaporation of the lymph-plasma-cytoplasm intraand inter-cellular fluids without surrounding tissue damage andgenerating a very clear cut. The far infrared radiation with awavelength of 100 microns vibrates the lymphatic, plasmatic andcytoplasmatic fluids inside the cells causing resonance of the samecells and therefore their fast explosion without any spreading of heat,results in no necrosis, less bleeding, insignificant tissue oedema, zeropostoperative pain, faster recovery, minimal possibility of cheloidformation, irrelevant damage to nerves and nerve endings. The thermaldamage is negligible and therefore accurate and rapid biopsies can beeasily performed.

FIG. 5 shows a macroscopic section of the cancer mass removed. To benoted are the well-preserved edges of the tissue. A uvula flap isprepared in FIG. 6 without bleeding using far infrared radiationirradiated by the electrode activated by electrothermic energy. FIG. 7shows the flap of FIG. 6 in loco with the arrows pointing to the uvula.The absence of thermal damage or ischemia in the tissue can be observed.FIG. 8 is a histological representation of connective tissue edge of aspecimen where the thermal damage is less than 6 microns (arrow).

FIG. 9 shows the soft-palate glandular tissue after removal using farinfrared radiation technology. As shown, the edges are free of thermaldamage and the glandular tissue is perfectly preserved (arrows show theedges). Absence of thermal damage is also seen in FIG. 10 and FIG. 11with the arrow respectively pointing to the edges of the superficialsection of the palate muscle. FIG. 12 is a photograph of a histologysection under 10× magnifications. Focal lesions of cytoplasmichomogenization with individual cellular loss. Measured by a semiquantitative method, wherein the ratio of the thermal damage in relationto the entire surface of the fragment, the fragment is focal and rangesfrom 2-5% as compared to being uniform. In FIG. 13, absence of thermaldamage can be seen at A-B, while the T area is affected by the cancer, alow grade polymorphic adenocarcinoma. In FIG. 14 the margin section ofthe superficial epithelium is shown with a thermal damage of less than 5microns.

The coagulation is effected in an ideal fashion by denaturisation anddestabilization of proteins, without burning vessels and surroundingtissue. During bipolar coagulation, the instruments according to theinvention work with absolute protection of the surrounding tissues;spots and halos are not present around the tips of the forceps becausethe coagulation happens exclusive inside the tips of the forcepseliminating any possibility of damage to the surrounding tissues.

As shown in FIG. 16 a forceps is used during coagulation in the sameoperation as shown in FIG. 15. The arrows indicate the precise point ofcoagulation which does not cause damage to the surrounding tissues.There is absolutely no “stick effect” and the temperature registeredduring the coagulation is below 55° C. It should be noted that thecoagulation speed is much improved as compared to that attained with anyother forceps currently on the market. The forceps as shown in FIG. 15were made entirely from the silver alloy according to the presentinvention and are here used during the clamping of a bleeding vessel toremove cancer of the larynx and perming a neck dissection. The forcepsis characterized by excellent elasticity, without damaging the vascularstructures, no stick effect, precise coagulation to the point withoutcreating thermal damage to the surrounding tissue to the vessel;

The silver alloy according to the present invention emitting farinfrared radiation is configured for medical, surgical and microsurgicalinstruments for treating biological tissues. The term “biologicaltissue” refers to any living organism and any substance found within, orderived from any living organism.

The Instruments according to the present invention induce such changesbecause the far infrared band radiant energy delivered to the biologicaltissue will be converted into vibrational phonon energy at a frequency,which is the same as or related to the incident far infrared radiation.This vibrational energy in the far infrared frequency range is received,stored and re-transmitted by bio molecules, in particular by themitochondria of the cytoskeleton. These instruments may be used toinduce phonon vibrations or modify existing phonon vibrations inbiological tissue. Such vibrations in the far infrared frequency of 100microns wavelength are sustained by and can be transmitted through thecytoskeleton. Hence, far infrared radiation could be a useful approachto trigger any number intracellular processes, such as intracellularsignalling. These instruments can deliver far infrared irradiation toDNA within living cells where the DNA is in the form of chromatin. Theseinstruments can deliver far infrared radiation to centrioles withinliving cells or to living cells in order to modify the activity of theDNA, or can deliver far infrared radiation to living cells in order tomodify the rate of DNA replication or deliver far infrared radiation toliving cells in order to modify rate of DNA transcription into RNA.These so manufactured instruments can deliver far infrared radiation toDNA and centrioles within living cells in order to modify a BoseEinstein condensate of phonons in the centriole and DNA of a livingcell. The instruments according to the present invention can facilitatethe induction of resonant effects in some systems at a specificfrequency. The optimum wavelength refers to a wavelength of far infraredradiant energy of about 80 to 120 microns and more exactly of 100microns. This wavelength is selected for its ability to elicit theexpected effect more quickly and efficiently than other frequencies, forits ability to evade absorption by hydro fluids and specifically toelicit vibrational energy in a specific article of biological tissue, orfor its ability to induce vibrational energy in water molecules orchains of water molecules as a method to enhance the coupling of the farinfrared radiation into a specific article of biological tissue.

The alloys of the present invention can be utilized in the followingapplications: medical, surgical and microsurgical fields. It can also beutilized in the following medical fields: oncology; oncological surgery;radio diagnosis and treatment; urology; ENT; cranio-maxillo facialsurgery; neurosurgery; neuroradiology; neuroradiotherapy; orthopaedicsurgery; orthopedics (from implants to the use of special electrodes);plastic surgery; osteogenetic distraction; cellular induction andstimulation; treatment of bedsores; aesthetic surgery; liposuction(utilizing specific cannulas which apply far infrared radiation touniformly reduce the quantity of fatty tissue without causing thermaldamage); resurfacing (application of far infrared radiation inanti-aging treatment of the face and body); synergetic application offar infrared radiation in cosmetic products; application of theelectrodes emitting far infrared radiation in augmentation or reductionmammoplasty; face-neck lifts; dental implants which take advantage ofthe therapeutic effects of far infrared radiation to activatemicro-circulation; treatment of tumors in the mouth area; treatment ofcataracts; treatment of lesions in the retina; treatment of cardiopathicischemia. Generally, but not limiting, the said invention possesses allthe characteristics of being applicable to all body tissues and in thefollowing procedures: cardio-surgery, also as implants; intravascular;arthroscopy surgery; urological, endoscopic chest surgery; laparoscopy;various heart; neurological; spinal.

EXAMPLE

The following sample alloys do not in any way constitute a limitationand are excellent for the creation of surgical and medical instrumentsaccording to the present invention: The contents (% by weight) of basemetals, germanium and acceptor dopants in the cast individual samplesalloys are as follows:

-   Sample 1: Silver-Germanium-Copper-Silicon=98:1.83:0.16:0.01-   Sample 2: Silver-Germanium-Gold-Silicon=98:1.83:0.16:0.01-   Sample 3: Silver-Germanium-Indium-Silicon=96:3.75:0.24:0.01-   Sample 4: Silver-Germanium-Gold=98:1.85:0.15

All the materials in alloys according to the present invention can bemade using conventional melting. One method for creating alloys inaccordance with the present invention consists in using the process ofrapid solidification (rapid cooling) utilizing a versatile combinationof base metals and additives. Another method consists in effectuatingmelting processes in microgravity conditions. Finally, an additionalmethod consists in melting all the components of the alloy by using highpressure. The term additive identifies germanium and acceptor dopants.

Alloys made in accordance with the present invention, be they binary,ternery quaternary, quinary or senary systems in composition yield asilver alloy material with new properties. Each alloy can be resoftenedby subsequent heating and quenching to yield the alloy in its originalblended state. Such a softened alloy can then be hardened again by asubsequent precipitation heat treatment. Another major characteristic ofthe silver alloys in accordance with the present invention is theirnon-toxic character. The alloy of the present invention is known to benon-toxic. The silver alloy can be a binary ternary, quarternary,quinary or senary metallic system, wherein two elements, germanium andsilver are always utilized.

The contents (% by weight) of silver, germanium, copper and silicon inthe cast individual sample alloy was as follows:Silver:Germanium:Gold:Silicon=98:1.83:0.16:0.01 (sample no. 2). Goldacts as a non-hydrogenic acceptor dopant. All the components are meltedin a high-frequency induction furnace using argon gas. The silver alloypossesses a fusion range (solidus-liquidus) of 870° C.-890° C. The alloyis age hardened till it reaches a hardness of 120 HVN, using thefollowing procedures:

-   a) heating to 700° C. for 30 minutes, and successively cooling in    water.-   b) treating at 250° C. for 120 minutes.

The above mentioned silver alloy contains in its matrix quantum dotp-type germanium nanostructured microcrystals and fully possesses theproperties of low capacitive impedance in relation to theelectrode-tissue interface and is able to emit electromagnetic farinfrared radiation with the wavelength in the range of 100 microns. Saidsilver alloy possesses a thermal conductivity superior to 0.35 W/cm.Kdegrees. This characteristic is the basis for elimination of any “stickeffect” on the tip of the electrosurgical instruments.

When using casting machines equipped with infrared sensing, the sensormust be calibrated for the said silver alloy as the components in thesilver alloy will give a false reading because the alloy emits farinfrared radiation.

The materials used in the alloy according to the present invention usingthe following method of fusion does not in any way constitute alimitation of the present invention: silver alloys having appropriatecompositions are melted using procedures conventially known in the priorart, for example, a high-frequency induction furnace using argon gas.The final alloys are then formed in the conventional manner to obtainthe final product. The alloy blend is then annealed for a predeterminedperiod of time at elevated temperatures. The temperature for the solidsolution annealing will vary with the composition of the compounds addedto the silver in the alloy. The suitable annealing temperature is onewhich will substantially soften the alloy. A range of temperaturesbetween 450° C.-800° C. is deemed to be useful. Optionally, it has beenfound that an annealing of 750° C. for 2 hours is best for subsequentlysuccessful hardening of the annealed alloy. Pre-alloying of germaniumwith silver improved the product. Furthermore, while 2 hours ofannealing time was considered optimum, the annealing time may be variedform 0.5 hours to 6 hours depending upon the variety and quantity ofmetals as well as the thickness. Subsequently, at the end of theannealing period, the solid solution of metals is rapidly cooled orquenched thereby bringing the alloy to ambient room temperature. Afterquenching, the alloy is preferably age hardened to obtain theprecipitation hardening effect. Age hardening comprises elevating thealloy to a temperature ranging from 150° C.-300° C. and maintaining thealloy at this temperature uniformly for a period ranging from typicallyfrom 0.5 to 24 hours. Lab testing has demonstrated that the optimumaging time and temperature is from about 205° C. to about 260° C. forone hour to produce the highest hardness in the alloy for mostembodiments according to the present invention. The age-hardened alloyis allowed to cool to ambient room temperature. It should be understoodthat the present invention comprises the making of silver alloyscontaining essentially germanium and optionally other metals subsequentto annealing the alloy and age-hardening the alloy. It should also beunderstood that the alloys according to the present invention maybework-hardened rather than age-hardened.

The ingots are homogenized at 250° C. to 700° C. for about ½ hr to 6 hrsand are then immediately subjected to hot working at a rate of at least30%, followed by water quenching and then milled. The alloys so obtainedare subjected to cold rolling to a thickness of about 40%, andprecipitate hardening and again at 250° C. to 600° C. The steps of coldworking and aging may be repeated so as to obtain the desired strengthand current conductivity. If necessary, the aged silver alloy in theform of strips, sheets, rods, wires, billets tubes and the like can befurther subjected to a small amount of cold working; however, eventuallythe amount of the additional cold working should be less than 40%.

The alloys can be utilized to laminate or partially and wholly coatmaterial cores which can be used for manufacturing said instruments.

The medical instrument can be made by coating them partially orcompletely with one or more of a material selected from the groupconsisting of biocompatible, insulating, semi-insulating elements,compounds and ceramic materials.

The alloy can also be made using conventional fusion methods andprepared by under high pressure conditions.

The alloy of the present invention can also be used to laminate, coat orbe applied to any kind of conductive and non-conductive material usingchemical processes. (e. g. non-electro plating) or chemical-physicalprocesses (e.g. electro-plating) or physical processes (e.g. thermalspray coating).

Clinical Cases

The following electrosurgical operative modes do not in any wayconstitute a limit and are excellent surgical procedures performedutilizing some instruments, such as electrodes and forceps, made usingthe silver alloy according to the present invention.

An operation to ablate a tumor of the soft palate of Mr. G. D., a75-year-old male was performed in Palermo on Feb. 5, 2003 by Dr. T. aplastic and cranio-maxillo facial surgeon. In order to perform thisoperation, a conventional power generator was used. The electrodes toperform the operation (FIG. 1) were made of a silver alloy material(Ag:Ge:Au:Si=98:1.83:0.16:0.1) and prepared according to the describedmethod. Under general anaesthesia, the palatal mucosal surrounding thetumour was infiltrated to the deepest layers and an incision wasperformed in the healthy tissue surrounding the tumour. The incision wasconducted up to the nose mucosal layer which was preserved. The tumormass was entirely removed (FIG. 3). The loss of substance was closed bya flap of elevator muscle of the palate and uvula (FIGS. 6 and 7). Themuscle plain was closed using vicryl, while nylon suture 5/0 was usedfor the mucosal plain. The tumor removed and the surrounding edges weresent to a laboratory for a histological exam.

Results: the patient awoke in a natural manner and from the start didnot complain of any post-operative pain. There were no signs of oedemaor pain in the area operated on.

Histological exams: Examination of the macroscopic specimens did notevidence thermal damage higher than 6 microns in the connective tissue.Regarding the tissue, muscle and glandular structure, thermal damage wasirrelevant nor were there alterations in the structure. The subcutaneousfatty tissue and vessels were intact. In none of the above-mentionedhistological exams was cellular damage caused by heat noted (FIGS.8-14).

Other clinical cases were successfully done to date.

The following four operations were performed by the same surgeon:

-   1. Excision of a cancer of the soft palate;-   2. Laryngectomy and neck dissection (FIGS. 15 and 16)-   3. Excision of cancer of the scalp infiltrating the skull-   4. Excision of cancer of the retro-molar region infiltrating the    tongue where a tongue re-section, partial hemimandibulectomy and    neck dissection were performed.

Office Procedures:

-   1. Uvulopalatoplasty (3 cases)-   2. Excision of Basal Cell Cancer of the face (3 cases)-   3. Excision of a cutaneous nevus (8 cases)-   4. Preauricular fistula removal-   5. Excision of a large, infected lipoma (8 cm×4 cm) in the gluteal    region;    -   In all the cases performed, it was noted that during surgery the        silver metal alloy materials offered the following        characteristics:-   1. No-stick effect of the prototype instrumentation used during cut,    cut and coagulation mode;-   2. No-stick effect of the forceps during coagulation mode;-   3. Ohmic contact with a low capacitive impedance in relation to the    electrode-tissue interface;-   4. Perfect cut with irrelevant thermal damage;-   5. High thermal and electrical conductivity;-   6. Possess perfect conduction and have anti-corrosion/anti-oxidation    properties;-   7. Are completely biocompatible;-   8. The silver alloy material according to the invention is far    superior in quality as compared to existing materials used to make    conventional medical, surgical, microsurgical and electrosurgical    instruments;-   9. Emission of far infrared radiation which gives the    characteristics of treating biological tissue during all operative    modes;-   10. Perfect coagulation, without thermal damage of the surrounding    tissue;-   11. Rapid coagulation in comparison to any other existing    instruments;-   12. Extreme versatility of the instrumentation realized with this    alloy.

With respect to point 9 of the above, intrasurgical emission of farinfrared radiation gives the surgeon the opportunity to treat theaffected area being operated on with beneficial far infrared radiationand with all related therapeutic effects used in medical, surgical,microsurgical, electrosurgical and physical therapy, orthopaedic,oncological and in all other medical fields.

The following was noted in all patients in the postoperative period:There was no post-operative pain, so pain killer or anti-inflammatorytreatment was not necessary. Post-operative condition was characterizedby rapid healing process without haematomas, oedema nor seromas and veryhigh patient satisfaction.

During the various operation phases, the far infrared radiation emittedby the quantum dot p-germanium nanostructured microcrystals act insynergy with the electrothermal energy provided by the power generatorand the anti-stick effect produced by the high thermal conduction of thealloy material in the presence of an irrelevant capacitive impedance dueto the electrode-tissue interface. Therefore it is possible to obtainperfect cell dehydration during surgical cutting. Based on what has beensaid and demonstrated, it may be claimed that the germanium containingalloy materials of the present invention are the most advancedtechnology for selective and ablative treatments of tumors.

All the above-mentioned patents and references are thereby fullyincorporated by reference and made a part of this disclosure. In thepresent invention, experience, studies and clinical evidence have beenpresented. Furthermore, hypothesis have been evidenced which attempt toexplain the real and effective results of the alloy material used in themaking of medical, surgical, electromedical, and microsurgicalinstruments applicable for humans, animals, biological and any organicelements.

The above describes the preferred forms of realization; however, otheralternative forms are possible. Other forms or variations in theinvention can be made by a skilled technician under the condition thatsaid forms or variations do not change in any way the original intent ofthe invention. Therefore, all photos, examples and descriptions must notlimit the intent of the invention which is integrated and defined by theattached Claims.

While the invention has been illustrated and described as embodied inmedical, surgical and electrosurgical instruments from special metalalloys, it is not intended to be limited to the details shown sincevarious modifications and structural changes may be made withoutdeparting in any way from the spirit of the present invention. Theembodiments were chosen and described in order to best explain theprinciples of the invention and practical application to thereby enablea person skilled in the art to best utilize the invention and variousembodiments with various modifications as are suited to the particularuse contemplated.

What is claimed as new and desired to be protected by Letters Patent isset forth in the appended claims and their equivalents:

1. An alloy for use in manufacturing medical, surgical, microsurgicaland electrosurgical instruments comprising: from 0.01% to 20% by weightof germanium; from 0% to 25% by weight relative to the germanium of atleast one of a non-hydrogenic and shallow hydrogenic acceptor dopant; upto 20% by weight of one or more of the compounds selected from the groupconsisting of platinum, gold, palladium, iridium, ruthenium, osmium,rhodium, niobium, tantalum, tungsten, aluminium, silicon, zirconium,rare earth elements including hafnium, yttrium and lanthanum; and as aremainder up to 100% by total weight constituted by silver.
 2. The alloyof claim 1, wherein the germanium content is less than 14.4% by weight.3. The alloy of claim 2, wherein the germanium content is at least 0.01%by weight.
 4. The alloy of claim 1, wherein the alloy has a hardness inthe range from 80 to 100 HVN.
 5. The alloy of claim 4, wherein thehardness is in the range of 40 to 149 HVN.
 6. The alloy of claim 1,wherein the acceptor dopant is one selected from the group of Group I,Group II and to Group III of the Periodic Table of the Elements.
 7. Thealloy of claim 1, wherein the p-type germanium is dispersed in the formof microcrystals in a matrix of the silver.
 8. The alloy of claim 1,wherein the non-hydrogenic and the hydrogenic acceptor dopants areselected from the group consisting at least one of gold, platinum,copper, gallium, indium, zinc, boron and their alloys.
 9. The alloy ofclaim 8, wherein the non-hydrogenic acceptor dopant is at least one ofgold and copper.
 10. The alloy of claim 1, wherein the weight ratio ofthe acceptor dopant relative to the germanium is less than 15%.
 11. Thealloy of claim 10, wherein the weight ratio of the acceptor dopantrelative to germanium is at least 5%.
 12. The alloy of claim 1, whereinthe germanium is present in the form of p-type germanium microcrystalsdispersed in a matrix of the alloy and capable of emitting far infraredradiation in the electromagnetic spectrum with a frequency range from0.1 to 4 THz.
 13. The alloy of claim 12, wherein the p-type germaniummicrocrystals dispersed in the alloy matrix are capable of stimulationto an emission of far infrared radiation from a source of energy. 14.The alloy of claim 13, wherein the energy is selected from the groupconsisting of sources of thermal energy, electro-thermal radiofrequency,body heat, ultrasound, microwave energy, laser energy, solar energy, DCcurrent, AC current, biological energy, chemical energy.
 15. The alloyof claim 1, wherein the alloy is resistant to processes selected fromthe group consisting of sulfurization, corrosion and oxidation.
 16. Thealloy of claim 1, having a hardness of HVN from 32 to 203 or moredepending on the use thereof.
 17. The alloy of claim 1, wherein thealloy is capable of emitting anions.
 18. The alloy of claim 1, whereinthe alloy possesses fractal surfaces.
 19. The alloy of claim 1, whereinthe germanium containing alloy exhibits a thermal conductivity above0.35 W/cm K. degrees.
 20. A process for producing an alloy fromcompounds suitable for medical instruments comprising the steps of:preparing a mixture from silver in the amount of up to 100% total weighttogether with from 0.01% to 20% by weight of germanium; at least one ofa non-hydrogenic and shallow hydrogenic acceptor dopant from 0% to 25%by weight relative to the germanium; up to 20% by weight of one or moreof the compounds selected from the group consisting of platinum, gold,palladium, iridium, ruthenium, osmium, rhodium, niobium, tantalum,tungsten, aluminium, silicon, hafnium, yttrium, lanthanum, zirconium;melting the mixture in a high frequency induction furnace using argongas to form a melt of alloy; casting the melt to form ingots of desiredsizes; solution annealing and quenching the alloy at a temperatureranging from 450° C. to 800° C. for a period of time between about 0.5hours to about 6 hours; and age hardening by heating the alloy at atemperature ranging from 150° C.-380° C. for a period of time between0.5 hour to 24 hours resulting in said alloy having a hardness in therange between 32 HVN to 203 HVN depending on the respective amounts ofalloy components.
 21. The process of claim 20, further comprising thestep of subjecting the melt to high pressure conditions.
 22. The processof claim 20, wherein the metal compounds are fused under conditions ofmicrogravity.
 23. The process of claim 22, wherein the melt undergoes arapid solidification after fusion.